EP0477859B1 - Probe using a mixed sub-electrode for measuring the activity of carbon in molten iron - Google Patents

Description

FIELD OF THE INVENTION
• This invention relates to a probe for measuring the activity of a carbon as a solute element containing in a molten iron.
BACKGROUND OF THE INVENTION
• With respect to metallic products, there have recently been many sorts, and the high grades of qualities thereof have progressed, and accordingly observations of the solute elements are important. Almost all of cases depend upon that analyzing samples are extracted and their concentrations are measured by means of instrumental analyses such as an emission spectroscope, but a problem involved therewith was that speediness lacks.
• In view of such circumstances, there have been made proposals as methods of rapidly measuring the concentrations or activities of the solute elements containing in the molten metals, at first of Japanese Patent Laid-Open 61-142,455 (Patent Laid-Open 61-260, 155, same 63-191,056, 63-286,760, 63-273,055, 63-309,849, 1-263, 556, 2-73,148, 2-82,153, Utility Model Laid-Open 63-109,643, and same 63-148,867). Basically, these conventional methods immerse, into the molten metal, a probe constituted by forming a coated layer made of an oxide (YOa) of a solute element (Y) or a composite oxide containing said oxide (YOa) on the outer surface of a solid electrolyte having an oxygen ion conductivity, and measure an oxygen partial pressure due to equilibrium reactions between the solute element (Y) and the oxide (YOa) through by the principle of an oxygen concentration cell so as to obtain the activities of the solute element (Y) (see also EP-A-0 295 112).
• However, problems thereabout arise that when the oxide (YOa) changes into a gas at a room temperature (e.g., CO, CO₂, NO₂, SO₂, etc.), it cannot be coated on the outer surface of the solid electrolyte, or when the oxide (YOa) changes into the gas (e.g., P₂O₅) at the measuring temperature, the coated layer fades away. On the other hand, it may be assumed as one of solving measures that the composite oxide (e.g., Ca₃(PO₄)₂, CaCO₃, CaSO₄, etc.) is employed. However, even in the methods utilizing the composite oxides, there exist no suitable substances stable until high temperature, for example, suitable nitrates for a case of a nitrogen sensor, carbonates for a carbon sensor, or sulfates for a sulfur sensor. For using the sensor in steel-makings, such oxides or composite oxides are required which remain stable as solid at the temperature of at least 1600°C.
SUMMARY OF THE INVENTION
• The present invention has been devised in view of the above mentioned problems, and is to offer a probe for measuring activities of carbon, which may be stable at high temperature.
• The probe according to the present invention for measuring the activities of the carbon in the molten iron is basically characterized by coating a sub-electrode (called as "mixed sub-electrode" hereinafter) which is composed of a mixture of carbide and an oxide (MOz) of other elements (M) than the carbon as a measuring object capable of constituting said carbides, on an outer surface of a solid electrolyte employed in conventional oxygen sensors.
BRIEF DESCRIPTION OF THE DRAWINGS
• Fig.1 is a cross sectional view showing one of examples which constitute the measuring element of a probe of the present invention;
• Fig.2 is a cross sectional view showing another example constituting the measuring elements;
• Fig.3 is a cross sectional view showing a further example constituting the measuring elements thereof;
• Fig.4 is a cross sectional view showing a still further example constituting the measuring elements of the same;
• Fig.5 is an explanatory view of a measuring method by means of a probe having an inventive constituent;
• Fig.6 is an explanatory view showing an outline of the whole probe; and
• Fig.7 is a graph showing correlated conditions between measuring results of a carbon sensor pertaining to the examples of this invention and analyzing results from sampling.
• 1 ... Mixed sub-electrode, 2 ... Solid electrolyte, 3 ... Reference electrode, 4 ... Lead wire from reference electrode, 5 ... Measuring element, 6 ... Lead wire of working electrode, 7 ... Potentiometer 8 ... Thermocouple, 9 ... Quartz tube, 10 ... Housing, 11 ... Connector, 12 ... Protective tube, and 13 ... Cap
MOST PREFERRED EMBODIMENT FOR PRACTISING THE INVENTION
• Explanations will be made to the measuring principle by means of the present probe.
• Assume that an oxygen is O, the carbon to be a measuring object is C, an element is M which constitutes the carbon and carbides, carbides of said C and M are MCx, and an oxide of M is MOz.
• Herein, suffixs "x" and "z" are stoichometric ratio of C to M, and O to M.
• When the probe which has the mixed sub-electrode containing MCx and MOz is immersed into the molten iron to be measured, under stated local equilibriums will be realized in a co-existing range of the mixed sub-electrode and the molten iron. $$\underline{\text{M}}\text{+ x}\underline{\text{C}}\text{= MCx}$$

  

  $$\underline{\text{M}}\text{+ Z/2 O₂ = MOz}$$

  

  
  If M is eliminated from the formulas (1) and (2), $$\text{x}\underline{\text{C}}\text{+ MOz = MCx + Z/2 O₂}$$

  

  
  Assuming that the equilibrium constant of the formula (3) is K, $$\text{K =}\frac{{\text{aMCx · Po₂}}^{\text{Z/2}}}{{\text{aMOZ · aC}}^{\text{x}}}$$

  

  
  Since K is the equilibrium constant, K is a function of the temperature only. If keeping constant the activity aMCx of MCx and the activity aMOz of MOz, an activity aC of C may be recognized by measuring a partial pressure Po₂ of O and the temperature of the molten iron.
• Thus, it is possible to measure the carbon by using the mixed sub-electrode of this invention, which could not be measured in the prior art, since a solid sub-electrode (coating) could not be obtained in the range of an iron melting temperature.
• Combinations such as SiC-SiO₂, Al₄C₃-Al₂O₃ or Cr₄C-Cr₂O₃ may be supposed as the substances for composing the mixed sub-electrode. Of course, such substances are not limited to these combinations, but are sufficient, if two substances forming the mixed sub-electrode remain solid at the using temperature and they are coupled such that the ratios of their activities are constant. A third additive may be participated.
• The mixed sub-electrode 1 may be formed by any one of methods coating it as shown in Fig.1 on the whole surface of the solid electrolyte 2 which may constitute the oxygen sensor; coating it partially as seen in Fig.2; in dotting as in Fig.3; and alternately with the solid electrolyte 2 as in Fig.4. In these figures, the numeral 3 designates a reference electrode, and the numeral 4 designates a lead wire from a reference electrode. By these illustrated constitutions, the co-existing range of the mixed sub-electrode 1 and the molten iron is formed in the molten iron to be measured, and the local equilibrium is formed.
• An explanation will be made to one example of the probes having the inventive composition, referring to Figs.5 and 6.
• In Fig.6, the numeral 6 designates a working electrode, the numeral 5 is a measuring element, and the numeral 7 designates a potentiometer. The measuring element 5 is composed of the solid electrolyte 2, a reference electrode 3, the lead wire from a reference electrode 4, and the mixed sub-electrode 1 formed as the coated layer. Basically, the composition is the same as those added with the mixed sub-electrode 1 as the coated layer in the conventional oxygen sensor. The solid electrolyte 2 is sufficient with any ones which have the oxygen ion conductivity at the high temperature and may be used to the conventional oxygen sensor. In the illustrated examples, the solid electrolyte 2 is shaped in tube, into which the reference electrode 3 is inserted.
• In the prior art, the solid electrolyte 2 is formed on the outer surface with the coated layer composed of the oxide (YOa) of the solute element (Y) to be measured or the composite oxide including said oxide (YOa), and is immersed into the molten metal for measuring, by the principle of the oxygen concentration cell, the oxygen partial pressure due to the equilibrium reaction between the solute element (Y) and the oxide (YOa), so as to obtain the activity of the solute element (Y).
• On the other hand, in the present invention, the coated layer is formed with the mixed sub-electrode 1 which is composed of the mixture of the carbide (MCx) and the oxide (MOz) of the other elements (M) than the carbon constituting said carbide (MCx), and is immersed into the molten iron for measuring, by the principle of the oxygen concentration cell, the oxygen partial pressure due to the equilibrium reaction between the carbon existing in the molten iron and the mixed sub-electrode 1, so as to obtain the activity of the carbon. Then, an electromotive force EMF is shown with a following formula. $$\text{EMF =}\frac{\text{RT}}{\text{F}}\text{ℓn}\frac{{\text{Po₂(II)}}^{\text{1/4}}{\text{+ Pe′}}^{\text{1/4}}}{{\text{Po₂(I)}}^{\text{1/4}}{\text{+ Pe′}}^{\text{1/4}}}$$

  

  
  wherein,

F:

Faraday's constant

R:

Gas constant

T:

Absolute temperature of the molten iron

Po₂(I):

Oxygen partial pressure of the reference electrode

Po₂(II):

Oxygen partial pressure within the local equilibrium zone

Pe′:

Parameter of partial electronic conductivity

• In the formula (5), since Po₂(I) and Pe′ are functions of the temperature, Po₂(II) may be recognized by measuring EMF and T. If Po₂(II) is substituted into the formula (4), the activity of the carbon to be the measuring objective may be known.
• In Fig.5, this working electrode 6 and the measuring element 5 are secured within a housing 10 together with a quartz tube 9 having a thermocouple 8 therein, and are connected to the potentiometer 7 via a connector 11. Further, the housing 10 is covered with a protective tube 12 and the actual probe is completed by covering the side of the measuring element 5 with a cap 13.
EXAMPLE
• The carbon sensor having the inventive structure was used for measuring the activity of the carbon in the molten steel. The specification of the used probe and the conditions of the molten steel are as follows.
     A material of the mixed sub-electrode
        a mixture of the carbide as SiC and the oxide (MOz) as SiO₂ of the elements other than the carbon constituting said carbide
     A material of the solid electrolyte
        ZrO₂ + MgO (8 mol%)
     A material of the reference electrode
        Cr + Cr₂O₃ (2 wt%)
     A method of coating the mixed sub-electrode
        A water and a water glass were added to the mixture of 1 : 1 (mol) of SiC and SiO₂ to form a slurry, and said solid electrolyte was dipped into this slurry and air-dried to form a coated layer.
     A measuring temperature
        1600°C
     A range of the molten steel composition
        %C = 0.01 to 1.0
        %Si = not more than 0.1
        %Mn = not more than 0.1
• Fig.7 shows the relation between EMF (the electromotive force) measured with said carbon sensor and the carbon concentration (%C) obtained by analyzing the sample.
• As shown in the same, a preferable relation could be obtained between EMF (electro motive force) to be measured with the present sensor and the carbon concentration (%C) obtained by analyzing the sample.
• A method of calculating the carbon concentration in the molten steel from EMF and the temperature to be measured by the present carbon sensor, is as follows.
• If the carbon sensor is immersed into the molten steel, an under mentioned equilibrium relation is realized, corresponding to the above formula (3) with respect to the mixed sub-electrode (SiC and SiO₂) and the molten steel surface. $$\underline{\text{C}}\text{+ SiO₂ = SiC + O₂}$$

  
• The equilibrium constant K₍₇₎ of this formula (6) is given by a following formular (7). $${\text{K}}_{\text{(7)}}\text{=}\frac{\text{aSiC·Po₂(II)}}{\text{aSiO₂·aC}}$$

  
• Further, K₍₇₎ of this formula (7) is given as the function of the temperature to a formula (8), and since SiC and SiO₂ are pure solids, respective activities aSiC and aSiO₂ may be regarded as 1, and the carbon activity aC may be calculated by measuring Po₂(II). $${\text{-RT nK}}_{\text{(7)}}\text{= 801400 - 192.56T (J/mol)}$$

  
• If the carbon activity aC is calculated and divided with the activity coefficient fc of the carbon of a formula (9), the carbon concentration may be obtained. $$\text{log fc = 0.243 x (Carbon concentration)}$$

  
• The above Po₂(II) may be obtained by a formula (10) from EMF and the temperature measured by the present sensor. $$\text{EMF =}\frac{\text{RT}}{\text{F}}\text{ℓn}\frac{{\text{Po₂(II)}}^{\text{1/4}}{\text{+ Pe′}}^{\text{1/4}}}{{\text{Po₂(I)}}^{\text{1/4}}{\text{+ Pe′}}^{\text{1/4}}}$$

  

  
  wherein

EMF:

Electro motive force to be measured by the present sensor (V)

T:

Temperature to be measured by the present sensor (K)

F:

Faraday's constant
   2.30521 x 10⁴ (Cal·V⁻¹ · mol⁻¹)

R:

Gas constant
   1.98648 (Cal·deg⁻¹ · mol⁻¹)

Po₂(I):

The oxygen partial pressure specified with the reference electrode Cr+Cr₂O₃
   Po2(I) = exp (18.636 - 86384/T)

Pe′:

Parameter of the partial electronic conductivity Pe′ = 10^{(24,42 - 74370/T)}

Po₂(II):

Oxygen partial pressure within the local equilibrium zone

Claims (1)

1. A probe for measuring the activity of carbon in molten iron, comprising a carbon measuring element (5) and a working electrode (6), said carbon measuring element comprising a solid electrolyte having an oxygen ion conductivity on an outer surface thereof and being coated with a mixture (1) of a carbide and oxides of elements other than carbon constituting said carbide.

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